JPS5945447A - Toner for developing electrostatic image - Google Patents

Abstract

PURPOSE:To obtain an electrostatic image developing toner capable of being fixed favorably by a heating roll fixing system, by using as a binder a graft copolymer obtained by graft polymerizing a vinyl monomer with a specified unsatd. polyester. CONSTITUTION:An unsatd. polyester is obtained by condensing an equiv. amt. of polyol with a mixture of polybasic acids consisting 5-90mol% unsatd. dibasic acid having an unsatd. double bond due to that between carbon atoms, and a polybasic acid, such as satd. dibasic acid. A graft copolymer obtained by graft polymerizing 99.8-90pts.wt. vinyl monomer with 0.2-10pts.wt. this unsatd. polyester is used for a binder, and an electrostatic image developing toner is obtained by dispersing a colorant and other toner component additives into the fine particles of this binder.

Description

[Detailed description of the invention]

The present invention relates to a toner for developing electrostatic images formed in electrophotography, electrostatic printing, electrostatic recording, and the like. In general, an electrostatic charge image is developed with a so-called toner consisting of a binder, a colorant, etc.) to form a toner image.
This toner image is transferred to the groove 1 or transfer paper.
It is fixed on L. Various methods are known for this fixing method, but the contact heating fixing method using a heating roller fixing device is superior in that it has higher thermal efficiency than the non-contact heating method between hot plate fixing bags, etc. It is preferable because it can settle in trenches at high speed. However, in this type of fixing method using a heating roller, the toner is actually softened at the heating temperature (°C As a technique to solve this problem, for example, as disclosed in Japanese Patent Application Laid-open No. 5+1-134652, a low molecular weight 11 polymer and a polymer-RTri combination are mixed. It is described that a toner having a binder made of a resin made of
, W + polymer containing f1, offset prevention property 1
Prevention of occurrence 1. k (T, times, f-type movement, but has a high softening point), and as a result, the fixing temperature is considerably high.
1. Na&J no shiku (J'determined/;"F cannot be performed, therefore, one piece of energy is required!"In addition to increasing the number of "1", additional J~111° is required to preheat the rollers. ) Question 17, further heating [1-A large heat resistance) ☆ and durability is 1 ≥ 6, there is a problem in practical use. To reduce the amount of water/C, if the proportion of low molecular weight H) polymer in the binder is increased,
If the anti-offset property is low, the glass transition point of the toner will be lowered and the toner will become unstable during storage. a: ÷ "inside"...and aggregates": becomes 9. On the other hand, Japanese Publication No. 51-23354 describes the use of a cross-linked resin as a binder of toner in order to prevent the offset phenomenon. Increasing the crosslinking density of the resin in the vagina to the 1i' degree required for this would increase the temperature required for fixing, creating the same problems as with the toner described above. Furthermore, since the resin has a three-dimensional structure, it is difficult to crush it, making it impossible to advantageously produce toner. Also, ``double/such polymer -ji'+,' ML
Polymer crosslinking is very hard, which causes warping and bending to the extent that it causes fatigue and deterioration of the heating roller when using toner as a component of the binder. [7] If the temperature of the heating roller is high and the heating roller is likely to cause the metal-onset phenomenon. 1M like this
In order to prevent the offset phenomenon from occurring at any moment, d
l. It is effective to supply mold release oil such as silicone oil to the surface of the heating roller, but the oil heats up and generates a certain amount of air, or contaminates the inside of the device, and the oil supply device , the structure of the fixing device becomes complicated. The object of the present invention is to overcome the above-mentioned drawbacks by electrostatic JJ having good fixing properties, excellent anti-offset properties, and therefore being more suitable for fixing than heated lawn fixing methods.
An object of the present invention is to provide a toner for developing R images. Other 11 targets 11 of the present invention, and still more highly non-cohesive targets
ii: (F image 3. The purpose is to provide a toso for μ image (]?).

[Ko/1. By condensing 4 and 1. vesicle A1 + poly-Zr cuticle/I-(1,2
~ L O weight M = part to pair (22, vinyl system 1i coalescence '19
．． 8-9 (1 weight!
By electrostatic charge image developer @/TI)ner! 7 achieved. Hereinafter, the present invention will be explained and explained in detail. In the present invention, r21.12, an unsaturated diIXK base acid having an unsaturated bond formed by a carbon-carbon double bond, and other polybasic acids, such as j Egg incubation-I JAA, #', acid toyoshi,
Quadruple 7 in which the proportion of the unsaturated dibasic acid is 5 to 90 moles
The famous painting Allu! - to obtain an unsaturated polynysdel, and 99.8% of the vinyl-based polynysdel was obtained based on 02 to 10 parts of the unsaturated polyester.
The 90-grained part was subjected to granopolymerization, and the thus obtained graft nail alloy was used as a gold binder, and its fine particles -
1. Dispersing colorant and other additives for toner components in f. This is used as a toner for electrostatic charge development. Since the toner of the present invention uses 1-'J and the above-mentioned graft nail combination as a binder, X //l as described below
! As is clear from the example, the effects and effects are different from 11I as follows. JJl et al., Ba-Ingu's Granod polymer contains 90 hk% or more of a vinyl-based single Jli component, so even if the fraction J'-1,1) is high, the softening point is 110. This is very low compared to resins with equivalent molecular weight. Since the softening point of the binder is low, when the toner of the present invention is fixed at a low temperature, -C also has high fluidity and high permeability into paper when melting at 1 ~, and therefore has a high permeability into paper. A great anchoring effect can be obtained with a ratio of 1 to 1.
After fixing, it becomes difficult to peel off from the paper. In addition, since the binder has a high molecular level, the toner of the present invention is strong, and after fixing, the toner forming the image is partially abraded due to friction.
The image is blurred on the hands, fingers, etc.: There is no ζ-1 attached/zeta, and the releasability when melting is quotient (-(heating
＞kc (tJ arrival J゛Konakana de Onosesoto)'
, Il: The occurrence of elephants is directly important. !・For p, graph t
□ tli: Combined tma molecule-chain form 7/, j4 It
It has relatively low elasticity 1,7, and thus the present invention Tono-1
, j1, the 4 toners of the paper that fall off after fixing will not crack or peel off. According to this toner, It is possible to reduce the constant danger of 1゛ by 447 per 1 person, and -15'J off ← Soto direct gravity 2'r: (j) ξ
Not only can it be done, but it can also be
”Hrr, Jj'j, minute existence-(E'?'l:
Since there is no necessary Q and 12, the 11ζλ property is small, and the following is true: Toner production [I',! During the crushing process, the ultrafine powder 1, which is undesirable in terms of scattering, is produced.
'Ir-is is small, toner yield is good
A loincloth is formed. In addition to this, there are the following advantages in Ming. That is, in the production of a binder, since unsaturated polyesters are susceptible to radical reactions, graft polymerization of vinyl monomers can be advantageously carried out with high efficiency. However, since an unsaturated polyester can be obtained by condensation of a polybasic acid containing an unsaturated dibasic acid and a polyhydric alcohol, the type and proportion of the unsaturated dibasic acid can be changed. 2) Depending on the molecular weight, density of unsaturated groups, etc. < indicates that various polyesters with different positions are obtained;
Therefore, it is important to select an appropriate unsaturated polyester, as well as the type of polyhydric alcohol. , it is possible to obtain a binder having the required properties, and as a result, it is possible to impart favorable properties to the toner. In the present invention, the unsaturated polyester, which is the raw material for the graft polymer used as the binder of the toner, is leftover from the unsaturated polybasic acid 1/:l: unsaturated dibasic acid having an unsaturated double bond, which becomes the grafting reaction point. It contains 5 to 90 molti, preferably 20 to 80 molti. When the proportion of unsaturated dibasic acid is less than 5 mole, the resulting unsaturated polynisdel has fewer grafting reaction points and -C
Vinyl system Qt of place + day ratio, F body whole graft T1
j cannot be matched and cannot be obtained.No.1. Since the graft polymer d has a low molecular weight, the toner using this graft polymer d as a binder has poor soil abrasion resistance and off-knit resistance. When the above ratio exceeds 00 mole, the graft polymer &-1 molecular part is huge and has a higher softening point than A) and 6. vinegar,
擢-tteto-neyoZ) )ノ一一- is constant λ"H'l"
No low Z. /F p:q an poly, -, r-, 7, chill ill,
Thousands of yen'rl! to: 'in is 1.00 (1-20
,0(] 0,fI+,l,to5,0(I r)=
, L Q, (] (i Q -r'; average molecular speed Mw is 3. fl fl ('l-・-30, fl
+10, f! ? 5, (to 10fl/20.rl
If the value of fl O is O) 11, and the value of MW/M mouth is r10 or more, it is lIf. Number 11', equal division -r [11-1. 〈1,000:1;ゝ1'
” If the orgasm minute 1,000t is small, it is natural that C1 minute-1
'l? A large graft polymer! 1. Toner t" Scratch resistance and offset prevention +l:
(If the molecular weight is high, the toner has a high fixing temperature.) The softening point of unsaturated polyester is 80 to 14.
It is preferably 0°C, especially 100 to 130°C.
-1, glass transition point is 40~90℃ 7i 5
Preferably, the temperature is 0 to 8()°C. Softening point is 8 (+
When using polyester, the glass transition point is less than 6t at 40℃.
If an unsaturated polyurethane gel with a softening point exceeding 140°C or a glass transition point/bar exceeding 90°C is used, the toner tends to become too hard and have poor fixing properties. be. The unspared polyester described in 1-1 is obtained by condensing a mixed system of an unsaturated dibasic acid and another polybasic acid, preferably a saturated polybasic acid, with a polyhydric alcohol. (Specific examples of acids include maleic acid, maleic anhydride, fumaric acid, citraconic acid, itaconic acid, etc.)
Used alone or in combination. Specific examples of suitably used saturated polybasic acids include &, t,
flL+, ge-atrac r1-phthalic anhydride, het acid, delag r1-r: fucuric anhydride, notalic anhydride,
Isonotal 6't Terephthalic acid, Endomethyl I/
(tetra) 11 drominhydro7thalic acid, detonhydride [1 notaric anhydride, hegyri 11 drosotaric anhydride, succinic acid,
Adipic acid, abilaic acid, -1j bacic acid, other saturated 21, rich 11 = acids, l-linolinic acid, trimellitic anhydride, bit1mellitic acid, u [++: water pyromellitic acid, other saturated The ξ that leaves the Taho V base acid is formed.
r1'c independent 1, mixed 1. It is used as Preferably used No. 1. Specific examples of polyhydric alcohols include Example Jk, 1: 7-dylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, cyfurobylene glycol, 17 glycol, 1,5-bentanediol, ], (]ibentanediol, opentyl glycol, hydrogenated bisphenol A1 ethylenic bisphenol A1 boriogycyprobyl/
Bisphenol A1 and other glycols, glycerin, and 1,000 other polyhydric alcohols.1. Q
i / ζ(ri 1 - Used by mixing, ru. A (Production of saturated polyester (・this time t, -r &
In addition to the above-mentioned indispensable ingredients, there are also molecules such as benzoic acid and other molecule-adjustable substances (J1 Compound J: consisting of anti-1,1-
1 catalyst young 1. <C1j, the reaction 111th agent is the addition hole) 1, manufacturing ψ= is the normal J So'hke usage size it J-r
, 1: < , the reaction is an inert gas 'p,', i lJi
For example, ltJ near, ', ゛λ degree about 2 ()
The reaction is carried out at 0° C., and the water that forms as a result of the reaction is removed by distillation under normal pressure or 11° C. into a container. The progress of the reaction can be tracked by successively measuring the acid value of the reaction product.The reaction is completed when the acid value reaches the desired value. 1!17 < L, teobarenoLrufu;1 (Japanese poly 1
′-, vinyl-based j, l for sprue! By subjecting the L-mer to a grafting reaction, a graft polymer serving as a binder for the toner of the present invention can be obtained. Here, the ratio of unsaturated polynisder and vinyl monomer is 0.2 to 10:99.8 to 90, preferably 0.5 to 8
:99.5-92. Specific examples of vinyl monomers include styrene, 0
-methylstyrene, 111-methylstyrene, p-, y
-y-rustyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-11-hexylstyrene, p-11-octylstyrene ,p-
n-nonylstyrene, p-n-decylsubrene, p-n
- Dodecylstyrene, p-methoxystyrene, ■) -
Aromatic vinyl monomers such as phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene; for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, imbupur acrylate, globil acrylate,
'Acrylic acid n-shaving del, acrylic acid dodecyl, -acrylic nit lauryl, acrylic acid 2-ethyl-＼gi/
Nisdelyl acrylate 9A, such as suderyl acrylate, 2-yl acrylate, phenyl acrylate, mepur α-chloroacrylate; mebyl methacrylate, ethyl methacrylate, 1
1 Bill, methacrylic acid! 1-phthyl, methacrylic 1
1 Kuitubupur, n-ocdyl methacrylate, dodecyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimebulaminoedyl methacrylate, methacrylic acid Methacrylic acid esters such as diethylaminol; vinyl chloride,
vinylidene chloride, vinyl bromide, vinyl fluoride, etc.
Vinyl rogens: vinyl acetate, vinyl propimenate,
Vinyl esters such as vinyl benzoate and vinyl acetate; others can be mentioned. The above vinyl armor may be used alone, but aromatic vinyl monomers, especially styrene monomers 6() to (1) may be used alone.
It is preferable to use 1% by weight of (1% by weight) in combination with 40 to 10% by weight of Nisder acrylates and/or methacrylic esters. In this case, the softening point is 1111%.
1. A graft polymer is formed which provides a toner favorable in terms of impact properties, anti-offset properties and non-cohesive properties. In other words, if the styrene monomer is less than 60%, the resulting graft polymer will be easily softened at low temperatures, and the toner will have high cohesiveness. %, the resulting graft polymer becomes hard and has a high softening point, resulting in poor fixing properties. The above-mentioned grafting reaction of a vinyl-based monomer to an unsaturated polyester can be carried out by a bulk polymerization method, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, etc. Among these, the suspension polymerization method is preferable. It's freezing. Il (I using the darkening method), 5th"? Then,
Usually 0.1 to 5 weight: Using 60 to 90 weight M4 parts of water containing an Ilt dispersion stabilizer as a medium, unsaturated polyester, polymerization catalyst, molecular F1 regulator, etc. are dissolved in a vinyl monomer. 40 to 10 needles of the 714 polymer solution obtained by
The reaction is carried out in a state where the body solution is suspended in the form of fine particles. The reaction temperature is 50 to 12°C (1°C), and after the completion of the reaction, the dispersion stabilizer is removed from the solid by washing with water and 1°C. As a polymerization catalyst in this grafting reaction, for example, peroxide Peroxide polymerization initiators such as benzoyl and lauroyl peroxide, azo polymerization initiators such as azobisisobutyronitrile, and other polymerization initiators are used at a ratio of 0.1 to the monomer.
It is used in the range of ~10 weight. Further, as the molecular weight regulator 7, for example, dodecyl mercaptan, butyl mercaptan, etc. are used in a range of 0 to 1.0'ilt relative to the monomer. Furthermore, in order to make the polymer have an entirely three-dimensional crosslinked structure by grafting, a crosslinking agent can be added to the reaction system. Compounds having 6 or more double bonds, such as divinylbenzene, divinylnaphthalene, derivatives thereof, and other aromatic divinyl compounds; such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, and other double bonds. Carboxylic acid esters having 1 or more carbon atoms; and others can be mentioned, and the amount used thereof is in the range of 0 to 10% by weight based on the monomer. The polymer may be contained as a main component, and other resins may be contained in an amount of less than 50% by weight of the entire binder. Polyurea, epoxy resin, phenolic lumen resin, and others are available, and these are
German or two types of Jji, upper mixed, and can be used once a month. Before t1-1 grafting t'coalescence C: l, the temperature is 140°C - it is preferable that the melt viscosity is 1.0-10 voices. If the melt viscosity exceeds 107 voids, the constant j7'r working temperature will not only increase. , anchoring effect on paper!Small scales and potash, fixation) impair the time-resistance ・r cm- and noni fr, i3.Toner of the present invention II1, colorants and other substances are added to the binder of 1-4 below. Contains additives, including colorants.
, unreasonable j71i 4'ljj had Q; 1, the dye can be used in the 2nd generation. Colorants and I- include carbon black, nigrosine dye (C, T, 504], 513), aniline blue (C
, 1, Bian 50405), Calco Oil Blue (C, I
. yfi azocc Blue 3), Rio no\i, :1rn- (C, 1, A14090), Ultramarine Blue (C, LA77103), DuPont Oil Red (C, I boiled 2 (i105), Quinoline Yellow o- (C
,'1. Thickness 4700! 'i), methylene:/blue chloride (C, 1, A 52015), lid 11 cyanine blue (C-Li674160), 7 laccite green oxalate (C, T, A42ono), Langzukku (C, L, ai 772 (3G), "
+-, Zoo゛ζ'gar ((ko, 1 boiled 4543!5),
and JL et al.'s d, is combination'1 jig, -zo's fil is no
can be given. Colorant U'1,]'j
l＞End 1゛ Toner as a single product”? Approximately 3 to 20
Contains IJ in a proportion such that it will be contained in a proportion of 'Wm':,. If the magnetic powder is included as described later, the magnetic powder can be used as a part of the entire colorant. When using it as a toner (・yo,
The magnetic powder in the toner is audible, but the magnetic material is a substance that is strongly magnetized in that direction by the magnetism (Jd).
Preferably, it is black in color, has high dispersibility in resin, is chemically stable, and can be easily obtained in the form of fine particles with a particle size of 1 p or less. 7 to 11
The most preferred are iron dioxide. Typical examples of materials that can be magnetized include metals such as cobalt, iron, and nickel; antimony, helium, bis-7
Alloys of metals such as sulfur, cadmium, calcium, chloride, titanium, tungsten, vanadium and their materials; Aluminum oxide 11ij
Metal oxides such as iron pentoxide, copper oxide, nickel oxide, +1li-lead oxide, butane oxide, and -7g/m oxide are found in all metal oxides including 11~&c7+1. . These (+B 'l'l' inclusion 141
is 11 Kawai, which is 40 to 70 weights of tiger'-L. Toner of the present invention & J-1 history, 1st I, direct heavy cutting, Greborimer, Jll"f electric control I, liI agent, flow jjl)
The glue can be made by adding a curing agent or a liquid R4-resin. Examples of off-setting inhibitors include low molecular weight polymerfins, with a number average molecular weight of 500-10.0 (10) and a softening point of 100-180'.
C is preferred. The toner of the present invention can be manufactured using a conventionally known method, for example, by kneading toner materials using a heated roll, heated extruder, etc., followed by cooling, pulverization, and classification. It is possible to build J.
1 details and 1
In , the softening point is the Koka type flow tester 1'-C.
FT-500 model (manufactured by Shimadzu Corporation), the measurement conditions were: load 20K17cm, nozzle diameter 1mm, nozzle length 111111mm. Preheat at 80℃ for 10 minutes.
S in the flow tester's plunger drop star temperature curve (softening flow curve) when measured and recorded as the column temperature rate ℃/min and [7. When the height of the curve is h, the temperature is h/2. The term "melt viscosity" refers to the viscosity YI calculated by the following formula using the same measurements as above and using the data. 11:1 Generation J1 Nika (RL, YNC 7cm) 1J
:Length of nozzle (,n) 1(,:Half of nozzle ↑A((・rn) 4＼t Tour I7, Δ: /Linda's 11no 11f10
1j (11n)/\X, : ? li-11-
ri((In), het: (Rule'Ii:iIt;'1
Gala again; <++! +< , -f/! ; point and V, differential scanning heat;; 1 cry [low temperature I) s
'5 Kisha Hr2) 6 Jll I, +I'? ! 1
．． ', speed 1asl 1o℃/min C measurement'JJI l/y
In this case, in the cuff transition territory war, the 9th melon length line and the base line from the glass transition point of J)
The maximum slope from -Rino\N-Nigashi 11 city to BeeRino's point is noto, and the temperature of the father point with the -j tangent is noj.
This value is defined as the 5th transition point. The values of the average molecular weight Mn and weight average molecular weight Mw of a polymer can be measured by a random method, and may vary slightly depending on the measuring method. Specification 91: (In rc, Mn and Mw are defined as values obtained by the following measurement method. In other words, each of these values is determined by gel vermi- sion or chromatography (GPC). ) under the conditions described below. At a temperature of 40°C,
The solvent (tetrahydrofuran) was flowed at a flow rate of 2 ml per minute, and the tetrahydrofuran concentration was 1.5 me75 me.
Inject 3mf of furan sample solution in terms of sample volume I to 1l
Ill do all the work. When measuring sample molecules tj)
11. The molecule -tt of the sample is several times 11'! ,
1.Created from dispersed polystyrene standard sample. Select measurement conditions that fall within the range where the logarithm of the bar and the count number are a straight line. , B S 706 boristyrene 8 quasi-samples (Mn = 1: (,7X], 0. Mw = 28.
Confirm with Ca which is 8x 10 J. Any GPC column used in the above may be used as long as it satisfies the conditions listed above, but for example, "TsK-GELJ", "QMIXl16 J
(manufactured by Tokukaitatsusha). The image forming part to which the toner of the present invention is applied may be any material capable of retaining an electrostatic image on its surface. 7
) 14 bodies, curved lead oxide, if machine semiconductor dispersed 1. Compound A is coated on a conductive substrate and used as a light guide for photoreceptors, etc.
A dielectric recording material such as a dielectric recording material coated with an insulating resin on a conductive support may be used. For example, in order to form an image-forming pressure band 1 (1) using a charger, the surface of the material is stirred and subjected to image-like FN light. Image formation (qlS 4A to il'i
Ground static electricity 4 (methods of forming workpieces, etc. are not used.
: ii Star 1, Su 1, but Tono L et al. 10th Thursday Uhe 1, January is 1st Sawa 5; Actual test 11 Example 1 Temperature Fi+, 4'', 'i stirrer, force' introduction tube and flow-1
・Equipped with a 1'-'h-in 3 t four-dock flask, polymegisino L'l pyrene-2
, 2-bis(4-hydroxyphenyl)propane 1,7
After adding 21' (5 moles) and introducing nitrogen gas from the gas introduction tube to create an inert atmosphere inside, the temperature was 50°C.
Prephthalic acid 622.5y (3.75 mol),
A mixture of 145r and maleic acid (1.25 mol) was added into the container, and then the temperature of the system was raised to 200° C. and a reaction was carried out for 6 hours. Water generated as the reaction progressed was removed by lapping with condensate. After that, the gas introduction pipe and condenser were removed, a vacuum line equipped with a trap was connected, and while the generated water was removed by the trap with reduced IEr, the reaction was further carried out at a temperature of 200°C for 6 hours.
This produced 9-unsaturated polyester A. The glass transition point of this unsaturated polyester is 68°C, the softening point is 1
05°C, acid value 15. Unsaturated polyester A 2-melting part styrene
80 parts]) 1 part n-bugol acrylate 20 parts benzoyl peroxide
A graft composition was made comprising 4 parts by weight or more of the material. On the other hand, a closed one-piece unit equipped with a stirrer, temperature side and gas inlet pipe.
In one flask, double-prepared phosphoric acid and 0.
．． Introducing 800% of water containing 1-b1 surfactant into gas? ? Shift composition 2121 was added and suspended in a nitrogen gas atmosphere through a nitrogen gas atmosphere in the container, and then ? 11i' 1 degree to 80℃ and about 8
It took 15 hours. After the reaction is complete, cool the system to 1 Jtl.
1 Separate the mold and wash with water: dry on top 12
, JJ, -) Ter'raft polymer Iff (41pξ.This graph) 11<softening point of coalescence I):, l: 130
℃, the glass transition point was 64℃≦). Graft polymer I 100 parts [0 parts Carbon black [Mogul ■・-11, 0 parts FA part Volip I]
] Vine 1/N 1-Viscol 660 P J After kneading 2 parts by weight or more of the substance in a ball mill for 61L'i, kneading it at a temperature of 130 °C for 1 hour in two 1-L'i, and after cooling, a soul-like body. The toner 1 of the present invention having a semi-uniform particle size of 1 micron was produced by completely crushing 12, finely pulverizing with a jet mill, and classifying.Examples 2 to 8 and Comparative Examples 1 to 4 Vesicles in Example 1 According to the manufacturing method of Polygo Steel,
According to the composition shown in Table 1 below, unsaturated polyesters B-G of d16 (tun) were produced (7).
According to the conditions shown in Table 2, the real M! A total of 11 types of graft polymers ■ to ■ were obtained according to the method for producing a graft polymer in Example J 1, and a total of 11 types of graft polymers were obtained according to the method for producing a toner in Example 1 using each of the graft polymers. 7
Separate inventive toners 2-8 and comparative toners 1-4 with a total weight of 41.1N were prepared. In Table 1, "molti" refers to vesicles fl in polymonocarboxylic acids.
The number of moles of the basic acid in Table 2 is the "proportion" of the unsaturated polyester in the graft assembly composition, r', rGJ is the glass transition point, r
Tm' J ld Softening point! e ”＊'G iy L
, Hek f+'i lrc are values corresponding to a temperature of 140°C. Regarding substances, abbreviations &i are as follows. POPP: Polyoxyglobylene ~ 2,2-t varnish (
4,4-Hydroxyphenyl) 1/8 people: n-butyl acrylic l/- 13MA: o--butalmethacrylate It was obtained as described above.Toner of the present invention and comparison toner 1
A developer was prepared by mixing all of 195 parts by weight of iron powder carrier in a 51i*J measuring unit for each of the above-mentioned developer materials, and a fixability test, an offset test, and a cohesiveness test were conducted using each developer. The results are shown in Table 3. In the fixation test, formation 1 was performed using the normal electrophotographic method.
-An electrostatic charge image is created by two series of developers! After the development, the obtained i+- toner image is transferred onto a transfer paper, and a heated roller whose surface layer is made of Tear-On (Bolif'trafluoroethylene, manufactured by DuPont) and a heated roller whose surface layer is made of silicone rubber [K
Using a fixing device equipped with a compression roller consisting of E-13001L, 'J'', V, J (manufactured by Shin-Etsu Chemical Co., Ltd.), the linear speed was set to 150 W/sec and the cola was heated to various temperatures. The toner image is fixed by setting the heating roller at a constant contact 'iTJ-enabled minimum temperature'.
I asked for IFF. In the offset test, the toner image obtained in the same manner as in the fixing test was transferred to a transfer paper, and after the toner image was fixed by the above-mentioned fixing device, a blank transfer paper was transferred under the same conditions. The operation of checking whether an offset phenomenon occurs or not by feeding the paper to the operating fixing device and observing whether 1ner stains occur on the transfer Ijf paper of C is carried out as in the previous Re. Heating [I changed the cola temperature setting variously and it became TL. And the lowest set temperature at which the offset phenomenon occurs in °C (lowest temperature at which offset occurs i!ll'1
The degree 'J'o) was calculated. In addition, in the cohesion test, each of the above-mentioned developers was placed in a near L container and placed in an atmosphere at a temperature of 55° C. for 2411 minutes to check for cohesion. Note that TFI is the minimum temperature at which the image area can be fixed even if the copy image is rubbed with paper of the same type as the transfer paper, and TF2 is the lowest temperature at which the image area does not collapse even if the copy image is rubbed with paper of the same type as the transfer paper. This is the lowest temperature at which no toner peeling occurred. As is clear from the above results, the toner t of the present invention has excellent fixing properties, anti-offset properties, and non-agglomeration properties. Procedural amendment (spontaneous) December 9, 1980 Director General of the Japan Patent Office Kazuo Wakasugi 1 Indication of the case 1982 Patent application No. 155822 C; 2
Name of the invention Electrostatic, unloading and developing toner 3 Relationship with the person making the amendment Patent issuer 7 II l/J 11-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo y Rikat C127) Roku Konishi ¥ Shinji T-gyo Co., Ltd. Name (first name (?j,) 4 Agent 5 h old■゛Instruction + l fl 6h old 1": riincrease) Number of inventions 7, subject of 'mi stop Column 8 for detailed explanation of the invention in the specification Contents of amendment ■ rlBm15mJ in the 7th line of page 22 of specification T14 is changed to 11
5mg/5meJ and d1 stop.

Claims (1)

[Scope of Claims] 1) A polybasic acid containing an unsaturated dibasic acid having a mole ratio of 5 to 90 and a polyhydric alcohol are condensed to form a polyhydric alcohol. To 41 parts of unsaturated polynisdel 02 to 10, vinyl-based, f'+ is grafted to fan body 99.8, ii, 90 parts are graft-polymerized, and the resulting graft nail union is used as a binder. A toner for developing electrostatic images characterized by: 2) Kraft@intermediate has a softening point of 120 to 160°C and a glass transition point of 50 to 80°C, 71+5 f+
-Claim No. 1 R-H+2 toner for developing electrostatic images. 3) Non-tl'η polynisal has a number average molecular weight of 1000 to 1.5 (10 (1) and a weight average molecular weight -!i of 5 f) ( 10 to 30 (100) The toner for developing an electrostatic image according to Claim 1 or 21A. 4) The graft polymer has a melt viscosity of 104 to 107 voids at a temperature of 140°C. Claim 1
Item 211 (- or the toner for developing an electrostatic image as described in Item 3).